Method of treating hydrocarbons



Oct. 7, 1947. c. w. TYsoN ETAL 2,428,690

METHOD OF TREATING HYDROCARBONS Filed Deo. 27, 1940 nneA van fwn. A l lechmann/.w

Patented Oct. 7, 1947 METHOD OF TREATING HYDROCARBONS Charles W. Tyson, Summit, Donald L. Campbell, Short Hills, Homer Z. Martin, Elizabeth, and Eger V. Murphree, Summit, N. J., assignors to Standard Oil Development Company, a corporation of Delaware Application December 27, 1940, Serial No. 371,920

' 2 Claims. 1 The present invention relates to theart of refining hydrocarbon oil distillates, such as naphtha, gasoline, kerosene, gas oil, and the like, by contacting the said distillates in vapor phase with a solid treating material in finely divided condition, such treating material including substances such as clay, bauxite, and the like. More particularly our present invention relates to improvements in feeding the solid treating material to the treating zone without employing motivating means which involve Amoving parts, and our in-- vention is fully described in the following speciflcation and claims, reference being had to the accompanying drawing.

Prior to the present invention, it was known to treat a gasiform material with a solid matev rial or to cause the gasiiorm material to undergo a chemical change in the presence of a finely divided solidl material, and in these processes it was common practice to force the solid treating material into the treating vzone by means of screws, such as the well-known Fuller-Kinyon pump or star-feeders. Mechanical devices such as screw-feeders have not proved entirely satisfactory as solid feeding means because of excessive wear. Another disadvantage is that screws are lexpensive and when they are of the compression type, the power consumption necessary to actuate the screw is excessive and impractical for many commercial operations.

'I'he present invention will be best understood by reference tothe accompanying drawing which shows diagrammatically, a form and arrangement of apparatus in which the present invention may be carried into eiect.

Referring in detail to the drawing, reference numeral I represents a feed or supply hopper containing a finely divided solid material, such as bauxite, having a particle size substantially in the range of 1 to 80 microns. 'I'his bauxite is discharged from hopper I into an elongated pipe 2 where it is uniformly admixed .with a quantity of a gaseous material such as carbon dioxide, nitrogen, hydrogen, a normally gaseous hydrocarbon, or the like, through a plurality ofV branch pipes 3, 4, and 6, to-the extent that'each cubic foot of gaseous material is admixed with or contains therein -40 lbs. of bauxite in pipe 2. From elongated pipe or conduit 2, the bauxite discharges into pipe 9 and thereafter into a treating vessel 2 1, which preferably is of a vsubstantially greater diameter than the conduit 9. Before it discharges into treating vessel 1 gasoline vapors at a temperature of about 40G-950 F. are discharged through line 8 into the pipe 9 as shown. Treating vessel 1 operates at 0 to 500 Ilb. pressure and 400-950 F. On entering the upflow treating zone 1 oi' greater internal diameter than the pipe 9 the upward velocity of the vapors is decreased to 1/2 to 10 feet per second. Moreover, the upward velocityl of the bauxite is lower than that of vthe vapors due to a slippage or settling'eiect.4 As a'result ofthe foregoing, the bauxite remains for a greater period of time in the treating zone 1 than the vapors. A jiggling phenomenon thus takes place, with regard to the bauxite, in the treating zone, effecting an intimate contact betweenfthe gasoline and the bauxite whereby the content of sulfur, sulfur compounds and Vother undesirable constituents in the gasoline is substantially reduced and the octane rating is improved. The admixture of gasoline vaporsiand bauxite is discharged from the treating zone'through conduit I0 into a primary cyclone separator I2 in which separator the major portion of the bauxite contained in the vapors is removed. The gasoline vapors which may contain some bauxite which vwas not removed in cyclone separator I2 are withdrawn overhead through line I5 and thence' discharged into a second cycloneseparator 22 where substantially the remaining bauxite is removed and passes by gravity into receiving hopper I4.-

'I'he gasoline vapors substantially completely free from bauxite are withdrawn from cyclone separator 22 through line 23 and may be passed to condensing and stabilizing equipment (not shown). Any catalyst particles remaining in the gasoline vapors may be recovered as a slurry in the bottoms stream 5I from the fractionator Il! and returned to the catalytic system to the feed in line 8 via pipe 52 or through line 53 to line I Il. From hopper I4 the bauxite is discharged into an elongated pipe I6 similar to pipe 2, which pipe I6 is connected through pipe I1 to a regeneration vessel I8, which maybe of the same form and construction as treating vessel 1, Pipe I 6 is provided with a plurality of branch pipes 24, 26, and 28 corresponding to pipes 3, 4, and 6 carried by pipe 2, and these branch pipes 24, 26, and 28 are employed to deliver a gaseous medium such `of fouled catalyst. which is mixed with the fouled catalyst is prefas CO2, flue gas, steam, and the like into pipe I6 for the purpose of fluidizing the bauxite therein. The amount of gas introduced into the pipe will vary according to many factors, but ordinarily suflicient gas is introduced to cause the material at the bottom of pipe I6 to have a density of from 10-40 lbs. per cu. ft. At a point near the bottom of pipe I6 air is introduced into said pipe I1 through line 30. `,The air serves to reduce the density of the bauxite as did the hydrocarbon vapors in pipe 9. The suspension or mixture of bauxite and air passes upwardly through vessel I8 which, as shown, has a greater internal diameter than pipe I1 so that a slippage of the bauxite occurs whereby the bauxite remains resident in the regenerating vessel I8 for a longer period of time than do the gases. In the regeneration vessel I8 the oxygen present causes any carbonaceous or sulfurous deposits contained in the bauxite as a result of the treating operlation in vessel 1 to be consumed by combustion or oxidation. The temperature during regeneration is prevented from exceeding 1200 F. by the recycling of cooled regenerated catalyst, The recycled catalyst passes from hopper I to pipe `4l) in which the powdered material is fluidized by introduction of a gaseous medium through pipes 42, 43, and 44. The material ows out of pipe 40, mixes with air entering through pipe 3| and 1passes through cooler 46. This stream, together fwith the spent catalyst stream from I1, enters the burning zone I8. The'amount of regenerated catalyst recycled may amount to from 1 to 10 parts by weight of regenerated catalyst to 1 part The regenerated catalyst erably cooled to a temperature of about 500 F. The fouled catalyst ordinarilyl will be at a-,tem-

`perature of about 60G-900 F., particularly if it is obtained directly from the treating zone. The

air which is charged into the system through line 3D may be at ordinary atmospheric temperature. The pressure in the burning zone may vary from lbs/sq. in. gauge to say 500 lbs/sq. in. gauge. Under the conditions specified, the regeneration of the catalyst proceeds. The regenerated bauxite, together with the gases, rpasses upwardly through elongated pipe 3,5'into a cyclone separator 36 similar in construction to cyclone separators I2 and 22. The bauxite which is separated in cyclone separator 36 from the gases is conveyed by any convenient means (not shown) to hopper I. A good method of conveying the bauxite from separator' 36 to hopper I is to elevate the cyclone separator 36 sufficiently so that i the bauxite may flow by gravity to hopper I or l the powder discharge of the cyclone may be connected directly to the top of the hopper I so that the separated catalyst falls directly into the hop- `per. If desired, a second cyclone' separator and/or electrical precipitator may be employed to remove still further quantities of bauxite conl4 long periods before regeneration becomes necessary; part of the spent catalyst can be recycled kto the reactor by means not shown. This recycle catalyst can be heated so as to furnish the heat absorbed by the reaction.

' The operation lust now described in connection with the apparatus is merely one form or embodiment of the present invention and the process is applicable to'clay treating of hydrodevice, it will be understood that the'mechanical energy used to transport the materials results from the difference between the density in the fluidized catalyst pipe 2 and the density in the i reactor and pipes 9 and I0; that is to say, the

` product of the density times the height of the material in pipe 2 must obviously be greater than l the sum of the products of density times the height for vessel 1 plus the density times the lheight of pipes 9 and I0. In a process of the type just now described, that is to say, the bauxite y treating of gasoline in vapor phase, pipe 2 may have an internal diameter yQt about 4 ft. and a length of about 120 ft. Pipe 9 may be of similar diameter 'and the internal diameter of treating zone 1 is substantially greater than that of pipe 9, as indicated in the drawing and may, for example, amount to 12 ft.

Our process is not limited to the precise details hereinbefore set forth and numerous modificar tions thereof will readily occur to those skilled in this particular art. c

The term refining of hydrocarbon distillates as employed herein is intended to mean the puritained in the effluent gases discharged from sepai rator 36 through line 38 and this bauxite may be i returned to the hopper I.

The hot gases in linev 38 are preferably employed to preheat the gasoline to vaporization temperatures. Furthermore,

1 the system should be operated so as to take advantage of the heat content of the freshly regenerated bauxite; that is to say, the hot regen- 3 erated bauxite in separator'36 should be delivered immediately to hopper l and then discharged into treater 1 so that advantage may be taken of its heat content.

This process allowsthe catalyst to be used for fication of such distillates by the removal of objectionable impurities therefrom and is not intended to include cracking, reforming, hydrogenation, dehydrogenation, alkylation, isomerization, or other types of treatments in which the oil undergoes a definite Change in chemical compoj sition. The refining of oils as herein employed involves the removal of sulfur and nitrogen-compounds, color and gum-forming constituents, and other objectionable impurities.

We claim: 1. A process of refining low-boiling hydrocarbon distillates which comprises passing a stream of said hydrocarbon distillates in ,Vapor form upf wardly through a refining zone, maintaining'a vertical column of solid refining agent in finely divided form, maintaining a fiuidizing gas in admixture with said refining agent within said column to maintain said refining agent in a freely flowing, uidized state throughout the full length of said column, discharging the finely dividedr Y refining agent from the base of said column into said first-named hydrocarbon stream, controlling the velocity of the vapors passing upwardly through said refining zone to maintain a relatively dense, turbulent mixture of vapors and refining agent within said refining zone, maintaining said vapors in contact with the refining agent within the refining zone at a temperature and for a period sufficient to obtain a substantial purification of said vapors, thereafter separating the refining agent from the hydrocarbon vapors, maintaining a second vertical column of said` finely divided refining agent, conducting relining agent separated from said hydrocarbon vapors to the top of said second-named column, e

` maintaining a uidizing gas in admixture withthe refining agent within said second-named column to maintain said refining agent in a freely iiowing, fiuidized condition, discharging the refining agent from the base of said second-named column into CHARLES W. TYsoN. Donau: L. CAMPBELL. Hoi/ma z. MAR'IIN.

mlm v. MURPHREE; n

va stream o! gases separate and independent from s 6 REFERENCES CITED The following references are ot record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,121,258 Osterstrom et al. June 21, 1938 2,128,220 Cooke Aug. 30. 1938 2,231,424 Huppke Feb. 11. 1941 2,239,801 Voorhees Apr. 29, 1941 2,248,196 Plummer July 8, 1941 2,253,486 Belehetz Aug. 19, 1941 2,273,075 Weems Feb. 17, 1942 1,984,380 Odell Dec. 18, 1924 2,303,047 Hemminger Nov. 24. 1942 2,305,004 AHeinrninger Dec. 15, 1942 2,311,584 Munday Feb. 16, 1943 v FOREIGN PATENTS Number Country Date 328,649 Great Britain May 1, 1930 533,037 Germany Sept. 8, 1931 

